Several proposals involving solute effects, phase separation or quenched-in nuclei and heterogeneous nucleation have been advanced to account for the high nanocrystal density that evolves during primary crystallization in marginal glass-forming alloys, but recent crystallization measurements and kinetics analyses provide new evidence for the role of the as-quenched structure on nanocrystal synthesis. Here, isothermal microcalorimetry investigations and quantitative electron microscopy measurements including high-resolution imaging and electron spectroscopy analyses were performed on a model system at different temperatures well below the glass transition to monitor the nanocrystallization isothermally as a function of time. From the combined measurements, the size distribution and the transformed fraction can be determined with a high accuracy for extended ranges of temperatures and times. In addition, calorimetric measurements in the glassy, liquid and crystalline states of the model alloy serves to analyze, for the first time, the fragility characteristics of a marginal glass-former that presents an important parameter in the context of the kinetic stability of the material against premature crystallization.

The major mechanical shortcoming of metallic glasses is their limited ductility at room temperature. Monolithic metallic glasses sustain only a few percent plastic strain when subjected to uniaxial compression and essentially no plastic strain under tension. Here we describe a room temperature deformation process that may have the potential to overcome the limited ductility of monolithic metallic glasses and achieve large plastic strains. By subjecting a metallic glass sample to cyclic torsion, the glass is brought to the yield surface; the superposition of a small uniaxial stress (much smaller than the yield stress) should then produce increments in plastic strain along the tensile axis. This accumulation of strain during cyclic loading, commonly known as ratcheting, has been extensively investigated in stainless and carbon steel alloys, but has not been previously studied in metallic glasses. We have successfully demonstrated the application of this ratcheting technique of cyclic torsion with superimposed tension for polycrystalline Ti–6Al–4V. Our stability analyses indicate that the plastic deformation of materials exhibiting elastic–perfectly plastic constitutive behavior such as metallic glasses should be stable under cyclic torsion, however, results obtained thus far are inconclusive.

The stability of a Pd40Cu30Ni10P20 bulk metallic glass (BMG) against structural relaxation is investigated by isothermal and isochronal annealing heat treatments below and above its glass transition temperature, Tg, for varying periods. Differential scanning calorimetry (DSC) of the annealed samples shows an excess endotherm at Tg, irrespective of the annealing temperature. This recovery peak evolves exponentially with annealing time and is due to the destruction of anneal-induced compositional short range ordering. The alloy exhibits a high resistance to crystallization on annealing below Tg and complex Pd- and Ni-phosphides evolve on annealing above Tg.

Thermal properties of a number of new Ca-based bulk metallic glasses are reported and discussed here. The compositional range of the new metallic glasses follows the formula:

CaA(Y,Ln)B(Mg,Sn)C(Ga,Zn,Al,Ag)D(Cu,Ni)E,

where A ranges from 0.40 to 0.70, B = 0 to 0.25, C = 0 to 0.25, D = 0 to 0.35, E = 0 to 0.35, A+B+C+D+E=1, and Ln represents the La group elements. The alloys have been developed based on specific criteria predicted from Senkov-Miracle topological and thermodynamic models for metallic glass formation, which narrow the compositional range for searching new metallic glasses.

For the immiscible Cu-Ta and Cu-W systems, realistic n-body potentials are derived under an embedded-atom method through fitting the cross potentials to some physical properties obtained from ab initio calculations for a few possible metastable Cu-Ta and Cu-W crystalline phases, respectively. Based on the derived potentials, molecular dynamics simulations reveal that in the Cu-Ta system, 30 at. % of Ta in Cu is the critical composition for the crystal-to-amorphous transition in the Cu-rich Cu-Ta solid solutions, and that in the Cu-W system, amorphous alloys can be formed within the composition range of 20–65 at. % of W. Interestingly, amorphous alloys are indeed obtained by ion-beam mixing in properly designed Cu70Ta 30, Cu65Ta35, Cu60Ta 40, and Cu50Ta 50 multilayered films, while crystalline Cu and Ta remain in Cu75Ta25 multilayered sample, which matches well with the critical composition of 30 at. % of Ta predicted by simulation. Moreover, there have been experimental data, which are in support of the predicted composition range of the Cu-W system by simulations.

High throughput, thin film synthesis and screening methods have been developed to investigate potential bulk metallic glass (BMG) compositions. Physical vapor deposition (PVD) was used for sample synthesis. A novel screening tool was developed to measure changes in resistance vs. temperature of these thin film samples. Example data for 34 compositions in the Mg-rich region of the Mg-Cu-Y ternary system are presented.

We have examined the micromechanical behavior of in situ formed metallic glass composites by performing in situ high-energy synchrotron X-ray scattering during uniaxial compression. The load partitioning between the amorphous matrix and the reinforcing particles was examined by measuring the lattice strains in the crystalline particles during compressive loading. The crystalline particles yield in compression during loading followed by tensile yielding during unloading. The large elastic mismatch between the two phases leads to large residual strains after each loading cycle. The load partitioning was also examined with finite element modeling (FEM). The predicted von Mises effective stress in the crystalline particles from the FEM calculations compares well with the experimentally determined von Mises effective stress so long as the deformation is elastic in both particles and matrix. After the particles yield, the model predicts strain hardening of the particles that is not observed experimentally.

The viscous properties of the multi component Zr41.2 Ti13.8 Cu12.5 Ni10.0 Be22.5 bulk metallic glass forming alloy was studied above the liquidus temperature. A shear thinning behavior for the molten alloy has been discovered. The shear thinning behavior can be characterized as a power law fluid with a power-law index of -0.5. Additionally, at low shear rates and temperatures near the liquidus temperature a visco-elastic type response in the flow behavior is observed.

The thermodynamics of the bulk metallic glass forming Pd43Ni10Cu27P20 alloy were investigated with differential scanning calorimetry (DSC). The specific heat capacity of the undercooled liquid with respect to the crystalline mixture was measured in the DSC simultaneously with the enthalpy of crystallization over the entire supercooled liquid region. The enthalpy, entropy, and Gibbs free energy change between the liquid and the crystalline mixture was determined from the specific heat capacity data. The calculated enthalpy function closely matched the enthalpies of crystallization that were measured in the DSC, which verifies the validity of the thermodynamic model used. A small Gibbs free energy difference between undercooled liquid and crystalline mixture was found for decreasing temperature in Pd43Ni10Cu27P20 when compared to other glass forming alloys. This reflects a small driving force for crystallization when undercooling this alloy and is the main contributing factor for its high glass forming ability.

Nd80Fe20 alloys were prepared by copper mold casting and directional solidification (DS) to obtain a coarse microstructure, which can be identified unambigously. The mold-cast samples exhibit a fine globular eutectic structure and show high room temperature coercivity (∼ 5 kOe). Transmission electron microscopic (TEM) investigations reveal the presence of fcc (a = 5.32 Å) Nd-rich and nanocrystalline non-cubic Fe-rich phases. The directionally solidified (DS) samples exhibit large grains (composition close to NdFe2). The NdFe2 grains (formed in the DS samples) show clear magnetic domains with uniaxial anisotropy indicating that the NdFe2-type phase observed in the present samples is not a cubic phase. X-ray absorption spectroscopy (XAS) was used to analyze the local configuration around Fe atoms in the mold-cast samples. The XAS patterns do not match with the bcc and fcc standards, which supports the presence of NdFe2 phase with uniaxial symmetry in the DS samples.

Classical heterogeneous nucleation theory coupled with DTA data has been used to closely estimate the crystallization behavior of continuously cooled bulk metallic glass (BMG) alloys. Continuous cooling transformation and time temperature transformation diagrams of three BMG alloys, Zr41.2Ti13.8Cu12.5Ni10Be22.5, Cu47Ti33Zr11Ni6Si1Sn2 and Mg65Cu25Y10 alloys, have been calculated. The critical cooling rates Rc of three alloys were calculated to be 1.7 K/s, 242 K/s and 36 K/s for Zr41.2Ti13.8Cu12.5Ni10Be22.5, Cu47Ti33Zr11Ni6Si1Sn2 and of Mg65Cu25Y10 alloys, respectively, which match well with the experimental values. We conclude that heterogeneous nucleation is more favorable than homogeneous nucleation for the formation of crystals during cooling of BMG alloy liquids. Our approach can be applied to the analyses of crystallization kinetics of BMG alloys with a wide range of critical cooling rates during continuous cooling as well as isothermal annealing.

The local atomic structure of Al87Ni7Nd6 amorphous metallic glass was determined upon heating by neutron diffraction and the pair density function (PDF) analysis. Two isotopes of Ni with very different scattering intensities were used (58Ni and 60Ni) to separate the local environment of the transition metal. A distinct pre-peak observed in reciprocal space arises because of chemical clustering of Ni atoms. With increasing temperature the coherence length of this peak increases indicating an enhancement in atomic clustering. In addition, precipitation of Al metal is first observed at 200 °C with heating. Binary and ternary Al phases form as the temperature increases further to 500 °C although the majority crystalline phase is Al. The local atomic topology at the intermediate temperatures can be represented with a model that is a combination of the atomic structure at room temperature plus Al.

Glassy Pd41Ni10Cu29P20 was creep-tested in compression at constant true stress. The defect concentrations were shown to be reversible with reproducible kinetics. The results could be fit better with a defect creation rate that is proportional to the applied power density than with one that depends on the strain rate only. The dilatation mechanism for creation of free volume is inefficient in energy and generation of free volume.

The heating rate dependencies of the glass transition temperature of the Ni65Nb35, Ni60Nb35Sn5, Ni59.35Nb34.45Sn6.2, Ni60(Nb40Ta60)34Sn6, and Ni57Fe3Nb35Sn5 metallic glass forming alloys were investigated with a differential scanning calorimeter (DSC). The relaxation time for each DSC experiment was plotted versus inverse temperature and a Vogel-Fulcher-Tamman (VFT) type relation was fitted to the data. The fragilities of the alloys were characterized with the fragility parameter, D*, and the VFT temperature, T0, which are the fit parameters from the VFT relation. It was found that for the binary alloy D* = 6.2, for the ternary alloys D* = 11.0, and that for the quaternary alloys D* was between 16.4 and 19.0. The D* increases monotonically as the number of components in the alloy is increased. This trend is also seen in Zr based alloys.

Zr-based bulk metallic glasses are of increasing interest due to their excellent properties, e.g. high elastic limit or catalytic activity. For some applications (golf clubs, hydrogen storage) a good oxidation resistance is necessary; in other cases (catalysis) fast oxidation is required.

Zr-Pd melt-spun glasses are known to exhibit “catastrophic” oxidation even at temperatures far below their glass transition. However, the surface of as-cast amorphous Zr70Pd30 was found to be protected by a thin native ZrO2 layer, thus allowing only localized nucleation of the oxidation reaction at preferred nucleation sites activated by destruction of the native oxide layer.

Detailed cross-sectional SEM and TEM revealed a rather complicated microstructure of the oxide islands consisting of a lamellar structure of tetragonal and moniclinic ZrO2 with different Pd contents and embedded nanocrystalline Pd. There is also evidence for a Pd enriched reaction zone between the oxide cone and the glassy matrix.

In order to understand the influence of the structure on the oxidation, the behavior of the metallic glass was compared with that of a crystallized alloy or even coarse crystalline Zr2Pd. Coarse crystalline Zr2Pd was found to be rather stable against oxidation, but exhibit very fast oxygen diffusion along the grain boundaries followed by oxide formation deep inside the material. Grain boundaries in the crystallized Zr70Pd30 does not exhibit such a behavior.

The short-range order of stable and deeply undercooled liquids of Al13(Co,Fe)4 alloys forming polytetrahedral phases is investigated by combining the containerless processing technique of electromagnetic levitation with elastic neutron scattering. Partial structure factors were inferred from the diffraction data which allow an analysis of both, the topological and the chemical short-range order of these alloy melts as a function of the temperature.

Metallic glasses can form in certain Al-Gd-Ni alloys. Devitrificaion occurs on subsequent heating to intermediate temperatures and although some phases form as expected the crystal structures of others are less certain. This paper presents a summary of transmission electron microscopy (TEM) data acquired from four devitrified Al-Gd-Ni(-Fe) alloys. It is shown that the alloys exhibit nanocrystalline microstructures consisting of face-centered-cubic α-Al, binary Al3Gd, and ternary phases. An Al-(Gd,Fe)-Ni phase forms as rods and exhibits the orthorhombic Al19Ni5Gd3 structure. Plates of the rhombohedral phase Al23(Ni,Fe)6Gd4 are also present. Complex faulting is observed in both ternary phases.

Zr65Ni10Cu7.5Al7.5Ag10 bulk metallic glass with a diameter of 2 mm and a length of 50 mm was prepared by copper-mould casting. The metallic glass obtained follows two-step crystallization reactions with the initial formation of metastable quasicrystals from amorphous phase, followed by the formation of a stable intermetallic Zr2Cu from the post-formed quasicrystals. In this paper, the microprocess of the amorphous-to-quasicrystalline transformation of Zr65Ni10Cu7.5Al7.5Ag10 bulk metallic glass was studied in detail by TEM and high resolution TEM coupled with nanobeam EDX. It was found that the amorphous-to-quasicrystalline transformation in the present system does not follow the traditional nucleation/growth mechanism. Instead, it undergoes a series of inter-processes and follows the sequence of phase transformation of amorphous→FCC Zr2Ni →Tetragonal Zr2Ni → Quasicrystals. Nanobeam EDX revealed that atomic diffusion was involved in all inter-processes of the phase transformations, suggesting that the amorphous-to-quasicrystalline transformation in the present bulk metallic glass is a non-polymorphous reaction.

We report on ultra-high catalytic activity of high-density monodispersive Cu and Ni nanostructures fabricated by newly developed laser electrodispersion technique. In these structures the particle sizes are 5 nm for Cu and 2.5 nm for Ni (relative size dispersion is less than 20%). Due to fast cooling during particle formation Cu and Ni grains have amorphous structure. The catalytic activity of Cu-based structures were studied in chlorohydrocarbons transformations reactions, while Ni structures were tested in the reaction of 1-nonene hydrogenation. The measured catalytic activity vs. particle surface density dependencies exhibit a maximum corresponding to densely packed one-layer granulated films. About an order of magnitude increase in the catalytic activity is observed when increasing the dielectric permittivity of the reactant solution. It is suggested that the observed high catalytic activity is due to thermally activated interparticle electron tunneling, which results in the appearance of negatively and positively charged particles in densely packed granulated films.

Following a novel silver nanoparticles synthesis pathway, pre-synthesized silver nanoparticles (4.4 nm of average diameter) were deposited on a substrate of yttrium manganese oxide. The method takes advantage of the spontaneous reduction of silver 2-ethylhexanoate in dimethyl sulfoxide (DMSO) at 50° C. Sodium citrate was used as capping agent. Silver nanoparticles dispersions mixed with yttrium manganite were kept for several days, at room temperature, in an Erlenmeyer flask wrapped in aluminum foil. Pure yttrium manganese oxide was prepared by solid state reaction of stoichiometric mixtures. The characterization of the samples mainly involved X-ray powder diffractometry and electron microscopy. Magnetic susceptibility was measured using a Quantum Design MPMS-5S SQUID magnetometer. Two samples were prepared: (I) YMnO3/Ag (1×10-3 M) and (II) YMnO3/Ag (5×10-2 M). The Ag nanoparticles deposition of (I) was confirmed by an increase in the surface area and a qualitative elemental analysis for silver. In (II) <10 nm silver nanoparticles were clearly appreciated by XRD and images of High Resolution Transmission Electron Microscopy. The measured value of magnetic susceptibility of (II) is slightly larger than pure YMnO3.